Detergent compositions



DETERGENT COMPOSITIONS Al G. Peck, Normandy, M0,, assignor to PecksProducts Company, St. Louis, Mo., a corporation of Missouri No Drawing.Application February 4, 1952, Serial No. 269,890

2 Claims. (Cl. 252-152) This invention relates to detergent compositionsand more particularly to detergent compositions having excellent sudsingand cleansing action.

Briefly, the present invention provides a detergent compositioncontaining in combination an alkyl aryl sulfonate and an alkyl sulfonicacid compound.

Among the objects of this invention are the provision of improveddetergent compositions; the provision of detergent compositions whichpossess excellent sudsing properties; the provision of detergents whichretain their sudsing action even in the presence of soil; and theprovision of detergent compositions which form suds stable over extendedperiods of time. Other features will be in part apparent and in partpointed out hereinafter.

The invention accordingly comprises the products hereinafter described,the scope of the invention being indicated in the following claims.

There are numerous detergent materials and mixtures which are useful forcleaning, laundering and the like. Certain of these are effective in thepresence of hard water as well as soft water, but it has been found thattheir sudsing action varies depending upon other components which may bepresent and that the suds which are formed are markedly reduced with thepassage of time and particularly in the presence of grease soils.Although alkyl sulfates, which are the reaction products derived fromindividual higher molecular weight alcohols or from a mixture of suchalcohols, are widely employed for cleansing purposes, the suds formed bysuch detergents are not only unstable with the passage of time or withextended agitation, but in addition the volume of suds is greatlyreduced when brought into contact With soils such as grease soils. Thealkyl aryl sulfonates, as a class, are recognized as having poorerfoaming properties and foams which are less stable than the alkylsulfates. Although various efforts have been made to stabilize suchdetergents and improvement has been obtained in the stability of sudsformed, these suds have continued to be unstable in the presence ofsoils. Since the primary purpose of a detergent is to clean, thisunstability has provided a major disadvantage. Increasing the stabilityof the suds themselves apart from their stability in the presence ofsoils does not provide the solution.

In accordance with the present invention, improved detergentcompositions are provided which not only possess stability over extendedperiods of time but are unusually stable in the presence of soils,especially grease soils. The detergent compositions of this inventioncontain a water-soluble alkyl aryl sulfonate, for example an alkalimetal salt such as sodium or potassium, or a water-soluble alkanolamineor alkylamine salt or mixtures thereof. The pther component is an alkylsulfonic acid compound such 2,758,92 Patented Aug. 7, 1956 as an alkylamide sulfonate, an alkyl ester sulfonate, or mixtures thereof.

The alkyl aryl sulfonates which are useful in the present invention areof the type:

in which R is an alkyl group containing from six to sixteen carbonatoms, the benzene ring may contain inert substituents such as a loweralkyl group (for example methyl) in a position not otherwise occupied,and X is an alkali metal, an alkanolamine or an alkylamine group, forexample, sodium, potassium, triethanolamine, monoethanolamine, diethanolpropanol amine or a nitro parafiin such as amino methyl propanol.

The alkyl sulfonic acid compound may be an alkyl amide sulfonate of theformula:

. R2 RlC oft-omomsm-n; or an alkyl ester sulfonate 'of the formula:

R1CH2CH2SO3R2 In the alkyl amide sulfonate, R1 represents a hydrocarbonradical of an acid of the fatty acid series such as oleic, palmitic,laur-ic, or a mixture thereof such as is found in the fatty acids ofcorn, linseed, caster, cottonseed, coconut, etc. Also R1 represents talloil acids which are principally abietic acid (20 carbon atoms). Radicalscontaining from twelve to eighteen carbon atoms are preferred sincecompounds containing radicals having less than twelve carbon atoms ormore than eighteen carbon atoms have less desirable physical propertiesor are otherwise less useful. R2 representsan alkyl or cycloaliphaticgroup containing one to eight carbon atoms and R3 is an alkali metalsuch as sodium or potassium, or an amine which forms a water-solublesalt with the alkyl amide sulfonic acid.

In the formula for the alkyl ester sulfonate R1 repre sents a fatty acidradical such as olcic, palmitic, lauric, or mixtures of fatty acids suchas corn, soya, linseed, castor, coconut, etc. Also R1 represents talloil acids which are principally abietic acid (20 carbon atoms). Radicalscontaining from twelve to eighteen carbon atoms are preferred. In theformula, R2 is an alkali metal such as sodium or potassium.

In order to test the sudsing eifect of the compositions of the presentinvention, ml. of the solution to be tested was measured into a 1000 ml.graduated cylinder. The cylinder was placed in a water bath and thetemperature of the test solution was adjusted to F.:2 F. The solutionwas stirred thirty seconds and the foam was allowed to age thirtyseconds before a reading of the volume was taken. Alternate stirring andaging, each for thirty seconds, was then carried out until the solutionhad been stirred for a total of one hundred fifty seconds with a readingbeing taken after each thirty second period of aging. After the finalreading at one hundred fifty seconds, 5 ml. of grease soil (doubledistilled free fatty acid-Emersol 305) was added to the graduatedcylinder and the alternate stirring and aging steps were repeated untilone hundred fifty seconds of stirring time had passed. Readings of foamvolume were taken after each thirty second aging period. Since thestirring was carried out at a constant rate and since the temperature ofthe test solution was maintained constant, reproducible results wereobtained.

The detergent compositions of the present invention contain from to 80parts by weight of alkyl sulfonic acid compound as defined above and theremainder alkyl aryl sulfonate from the group described above. Thepreferred range is to parts by weight of alkyl sulfonic acid compoundwith the remainder alkyl aryl sul fonate while the specific ratio whichhas been found most desirable is 30 parts by weight of alkyl sulfonicacid compound and 70 parts by weight of alkyl aryl sulfonate.

The following examples illustrate the invention:

Example 1 A mixture was formed of 90 parts of the triethanolamine saltof dodecyl benzene sulfonic acid and 10 parts of sodiumN-oleoyl-N-methyl taurate, all by weight. An aqueous solution containing0.12% by weight of the mixture was formed and tested as described above.The average amount of foam when themixture was tested as describedwithout soil was 156 ml., while after addition of 5 ml. of soil of theaforementioned type, it was 55 ml. However, from the amount of foamafter soil was added to the individual components, it was calculatedthat the amount of foam for the mixture, after soil was added, would be31 ml.

The detergent mixture is effective both in hard and soft water for theefficient removal of soil, especially in the case of oil or grease soilsfound on hard surfaces such as dishes and floors and on soft surfaceslike textiles and even skin.

Example 2 Example 3 Example 1 was repeated but the mixture was formed of70 parts of the triethanolamine salt of dodecyl benzene sulfonic acidand 30 parts of sodium N-oleoyl- N-methyl taurate, all by weight. Theaverage of the amount of foam formed without soil was 164 ml., whilewith soil it was 89 ml. The calculated amount of foam, based upon theresults obtained with the individual components of the mixture, was ml.The detergent composition formed was effective for cleaning, especiallysurfaces bearing oil or grease soils.

Example 4 Example 1 was repeated but the mixture was formed of 60 partsof the triethanolamine salt of dodecyl benzene sulfonic acid and 40parts of sodium N-oleoyl-N-methyl taurate, all by weight. The average ofthe amount of foam formed without soil was 161 ml., while with soil itwas 69 ml. The calculated amount of foam, based upon the resultsobtained with the individual components of the mixture, was 37 ml. Thedetergent composition formed was effective for cleaning, especiallysurfaces bearing oil or grease soils.

Example 5 Example 1 was repeated but the mixture was formed of parts ofthe triethanolamine salt of dodecyl benzene sulfonic acid and 50 partsof sodium N-oleoylN-methyl taurate, all by weight.

The average of the amount of foam formed without soil was 156 ml., whilewith soil it was 67 ml. The calculated amount of foam, based upon theresults obtained with the individual components of the mixture, was 39ml. The detergent composition formed was efiective for cleaning,especially surfaces bearing oil or grease soils.

Example 6 Example 1 was repeated but the mixture was formed of 40 partsof the triethanolarnine salt of dodecyl benzene sulfonic acid and 60parts of sodium N-oleoyl-N-methyl taurate, all by weight. The average ofthe amount of foam formed without soil was 150 ml., while with soil itwas 73 ml. The calculated amount of foam, based upon the resultsobtained with the individual components of the mixture, was 41 ml. Thedetergent composition formed was effective for cleaning, especiallysurfaces bearing oil or grease soils.

Example 7 Example 8 Example 1 was repeated but the mixture was formed of20parts of the triethanolamine salt of dodecyl benzene sulfonic acid andparts of sodium N-oleoyl-N-methyl taurate, all by weight. The average ofthe amount of foam formed without soil was 153 ml., while with soil itwas '65 ml. The calculated amount of foam, based upon the resultsobtained with the individual components of the mixture, was 45 ml. Thedetergent composition formed was eifective for cleaning, especiallysurfaces bearing oil or grease soils.

Example 9 Example 1 was repeated but using parts of the sodium salt ofdecyl benzene sulfonic acid and 10 parts of sodium N-oleoyl-N-methyltaurate, all by weight. The test solution contained 0.12% by weight inwater and the amount of foam obtained in the absence of soil was 166 ml.After 5 ml. of soil had been added and the test continued as describedabove, the amount of foam was 57 ml. The calculated amount of foam inthe presence of soil, based upon the results obtained with theindividual components of the mixture per se, was 30 ml.

Example 10 Example 9 was repeated but using 80 parts of the sodium saltof decyl benzene sulfonic acid and 20 parts of sodium N-oleoyl-N-methyltaurate, all by weight. The test solution contained 0.12% by weight inwater and the amount of foam obtained in the absence of soil was 153 ml.After 5 ml. of soil had been added and the test continued as describedabove, the amount of foam was 65 ml. The calculated amount of foam inthe presence of soil, based upon the results obtained with theindividual components of the mixture per se, was 31 ml.

Example 11 Example 9 was repeated but using 70 parts of the sodium saltof decyl benzene sulfonic acid and 30 parts of sodium N-oleoyl-N-methyltaurate, all by weight. The test solution contained 0.12% by weight inwater and the amount of foam obtained in the absence of soil was 159 ml.After 5 ml. of soil had been added and the test continued as describedabove, the amount of foam was 87 ml. The calculated amount of foam inthe presence of soil, based upon the results obtained with theindividual components of the mixture per se, was 32 ml.

Example 12 I Example 9 was repeated but using 50 parts of the sodiumsalt of decyl benzene sulfonic acid and 50 parts of sodiumN-oleoyl-N-methyl taurate, all by weight. The test solution contained0.12% by weight in water and the amount of foam obtained in the absenceof soil was 135 ml. After ml. of soil had been added and the testcontinued as described above, the amount of, foam was 72 ml. Thecalculated amount of foam in the presence of soil, based upon theresults obtained with the individual components of the mixture per se,was 35 ml.

Example 13 Example 9 was repeated but using 30 parts of the sodium saltof decyl benzene sulfonic acid and 70 parts of sodium N-oleoyl-N-methyltaurate, all by weight. The test solution contained 0.12% by weight inwater and the amount of foam obtained in the absence of soil was 145 ml.After 5 ml. of soil had been added and the test continued as describedabove, the amount of foam was 73 ml. The calculated amount of foam inthe presence of soil, based upon the results obtained with theindividual components of the mixture per se, was 37 ml.

The detergent mixtures of the present invention may be employed incombination with neutral salts and alkali inorganic builder salts.

Example 14 A mixture was formed, as described in Example 1, of 90 partsof sodium dodecyl benzene sulfonate and parts of sodiumN-oleoyl-N-methyl taurate, all by weight. This was combined with neutraland alkali inorganic builder salts and an aqueous solution was formedcontaining 0.20% of the combined mixture. Of this, 0.016% was thecombination of the alkyl aryl sulfonate and acyl alkyl taurate while0.184% was the neutral and alkaline builder salts. When tested asdescribed in Example 1 without soil, 132 ml. of foam was formed. When 1ml. of soil was added as described above, the amount of foam was 5 3 ml.The calculated amount of foam in the presence of soil, based upon thetest results with the sodium dodecyl benzene sulfonate alone and thesodium N-oleoyl-N- methyl taurate alone, was 26 ml.

Example 15 Example 14 was repeated but using 70 parts of sodium dodecylbenzene sulfonate and 30 parts of sodium N- oleoyl-N-methyl taurate, allby weight. This was combined with neutral and alkali inorganic buildersalts and an aqueous solution was formed containing 0.20% of thecombined mixture. Of this, 0.016% Was the combination of the alkyl arylsulfonate and acyl alkyl taurate while 0.184% was the neutral andalkaline builder salts. When tested as described in Example 1 withoutsoil, 104 ml. of foam was formed. When 1 ml. of soil was added asdescribed above, the amount of foam was 50 ml. The calculated amount offoam in the presence of soil, based upon the test results with thesodium dodecyl benzene sul fonate alone and the sodium N-oleoyl-N-methyltaurate alone, was 27 ml.

Example 16 Example 1 was repeated but using 90 parts of thetriethanolamine salt of dodecyl benzene sulfonic acid and 10 parts ofpotassium N-oleoyl-N-methyl taurate, all by weight. The test solutioncontained 0.12% by weight in water and the amount of foam obtained inthe absence of soil was 160 ml. After 5 ml. of soil had been added andthe test continued as described above, the amount of foam was 45 ml. Thecalculated amount of foam in the presence of soil, based upon theresults obtained with the individual components of the mixture per se,was 31 ml.

Example 17 Example 1 was repeated but using 70 parts of thetriethanolamine salt of dodecyl benzene sulfonic acid and 30 parts ofpotassium N-oleoyl-N-methyl taurate, all by Weight. The test solutioncontained 0.12% by weight in water and the amount of foam obtained inthe absence of soil was 155 ml. After 5 ml. of soil had been added andthe test continued as described above, the amount of foam was 66 ml. Thecalculated amount of foam in the presence of soil, based upon theresults obtained with the individual components'of the mixture per se,was 36 ml.

Example 1 8 Example 1 was repeated but using 70 parts of thetriethanolamine salt of dodecyl benzene sulfonic acid and 30 parts ofthe sodium salt of coconut fatty acid-N-methyl taurine, all by weight.The test solution contained 0.12% by weight in water and the amount offoam obtained in the absence of soil was 162 ml. After 5 ml. of soil hadbeen added and the test continued as described above, the amount of foamwas 70 ml. The calculated amount of foam in the presence of soil, basedupon the results obtained with the individual components of the mixtureper se, was 44 ml.

Example 19 Example 1 was repeated but using 70 parts of thetriethanolamine salt of dodecyl benzene sulfonic acid and 30 parts ofsodium oleoyl isethionate, all by weight. The test solution contained0.12% by weight in water and the amount of foam obtained in the absenceof soil was 126 ml. After 5 ml. of soil had been added and the testcontinued as described above, the amount of foam was 58 ml. Thecalculated amount of foam in the presence of soil, based upon theresults obtained with the individual components of the mixture per se,was 30 ml.

Example 20 Example 1 was repeated but using 70 parts of themonoethanolamine salt of dodecyl benzene sulfonic acid and 30 parts ofsodium N-oleoyl-N-methyl taurate, all by weight. The test solutioncontained 0.12% by weight in water and the amount of foam obtained inthe absence of soil Was 161 ml. After 5 ml. of soil had been added andthe test continued as described above, the amount of foam was 75 ml. Thecalculated amount of foam in the presence of soil, based upon theresults obtained with the individual components of the mixture per se,was 43 ml.

Example 21 Example 1 was repeated but using 35 parts of themonoethanolarnine salt of dodecyl benzene sulfonic acid, 35 parts of thetriethanolamine salt of dodecyl benzene sulfonic acid and 30 parts ofsodium N-oleoyl-N-methyl taurate, all by weight. The test solutioncontained 0.12% by weight in water and the amount of foam obtained inthe absence of soil was 167 ml. After 5 ml. of soil had been added andthe test continued as described above, the amount of foam was 74 ml. Thecalculated amount of foam in the presence of soil, based upon theresults obtained with individual components of the mixture per se, was39 ml.

Example 22 Example 1 was repeated but using parts of the diethanolpropanol amine salt of dodecyl benzene sulfonic acid and 10 parts ofsodium N-oleoyl-N-methyl taurate, all by weight. The test solutioncontained 0.12% by weight in water and the amount of foam obtained inthe absence of soil was 154 ml. After 5 ml. of soil had been added andthe test continued as described above, the amount of foam was 42 ml. Thecalculated amount of 7 foam in the presence of soil, based upon theresults obtained with the individualcomponents of the mixture per se,was 29 ml.

Example 23 Example 1 Was repeatedbut using 70 parts of the diethanolpropanol amine salt of dodecyl benzene sulfonic acid and 30 parts ofsodium N-oleoyl-N-methyl taurate, all by weight. The test solutioncontained 0.12% 'by weight in water and the amount of foam obtained inthe absence of soil was 137 ml. After 5 m1. of soil had been added andthe test continued as described above, the amount of foam was 59 ml. Thecalculated amount of foam in the presence of soil, based upon theresults obtained with the individual components of the mixture per se,was 32 ml.

The synergistic effect of the combination of the allay] aryl sulfonatesand the alkyl sulfonic acid compounds is obtained regardless of the typeof soil involved.

Example 24 Example 3 was repeated but in lieu of the double distilledfree fatty acid, 5 m1. of hydrogenated vegetable oil Spry) was utilizedas the soil. The average amount of foam formed Without soil was 163 ml.,while with soil it was 92 ml. The calculated amount of foam, based uponthe results obtained with the individual components of the mixture, was59 ml.

In view of the above, it will be seen that the several objects of theinventionflarcachieved and other advantageous results attained.

As many changes could be made in the above products without departingfrom the scope of the invention, it is intended that all mattercontained in the above description shall be interpreted as illustrativeand not in a limiting sense.

1 claim:

1. The method of increasing the stability and volume of suds of an alkylaryl sulfonate-containing aqueous detergent solution in the presence ofgrease soil, comprising adding to an alkyl aryl sulfonate selected fromthe group consisting of the triethanolamine salt of dodecyl benzenesulfonic acid, approximately 10% to 50% by weight with respect to saidsulfonate of an alkali metal N-oleoyl-N-methyl taurate.

2. The method of increasing the stability and volume of suds of an akylaryl sulfonatecontaining aqueous detergent solution in the presence ofgrease soil, comprising adding to the triethanolamine salt of dodecylbenzene sulfonie acid, approximately 15% to 30% by Weight with respectto said sulfonate of sodium N-oleoyl-N-methyl taurate.

References Cited in the file of this patent UNITED STATES PATENTS2,088,085 Gross July 27, 1937 2,156,996 Martin May 2, 1939 2,283,199Flett May 19, 1942 2,477,383 Lewis July 26, 1949

1. THE METHOD OF INCREASING THE STABILITY AND VOLUME OF SUDS OF ANALKALY ARYL SULFONATE-CONTAINING AQUEOUS DETERGENT SOLUTION IN THEPRESENCE OF GREASE SOIL, COMPRISING ADDING TO AN ALKYL ARYL SULFONATESELECTED FROM THE GROUP CONSISTING OF THE TRIETHANOLAMINE SALT OFDODECYL BENZENE SULFONIC ACID, APPROXIMATELY 10% TO 50% BY WEIGHT WITHRESPECT TO SAID SULFONATE OF AN ALKALI METAL N-OLEOYL-N-METHYL TAURATE.